Growth and electro-optic studies in mixed (NH4) x K1−x H2PO4 single crystals

Single crystals and mixed crystals of KH₂PO₄ (KDP) and NH₄H₂PO₄ (ADP) were grown with different dopant concentrations of NH₄H₂PO₄ in KH₂PO₄ in solution by Holden’s rotary crystallizer technique. The effect of additives like Borax (Na₂B₄O₇·10H₂O), seed crystal rotation rate and qualities of the crystals were studied. The half-wave voltages (in longitudinal mode) for KDP mixed with 1% ADP (by weight) were found and hence the unclamped (low frequency) electro-optic coefficients (r ₆₃) were calculated for various wavelengths in the visible region of the spectrum. It was noted that the half-wave voltage increases with increase in wavelength and temperature.     

Electrical conductivity measurements on gel grown KDP crystals added with urea and thiourea

Pure and impurity added (with urea and thiourea) KDP single crystals were grown by the gel method using silica gels. Electrical conductivity measurements were carried out along both the unique axis and perpendicular directions at various temperatures ranging from 30 to 140‡ C by the conventional two-probe method. The present study shows that the conductivity in KDP crystals, for both the impurities considered, increases with the increase in impurity concentration and temperature. Activation energies were also determined and reported.     

Investigation on (100) face of KDP crystal poisoned by MoO4 2? impurity

Potassium dihydrogen phosphate (KDP) single crystals doped with molybdate (MoO₄ ²⁻) were grown via the conventional temperature cooling and rapid growth methods, respectively. MoO₄ ²⁻ made KDP crystals tapering for conventional temperature cooling method. When KDP crystals were grown by rapid growth method, MoO₄ ²⁻ could induce liquid inclusions and simultaneous crystals. The measurement on growth rates indicated that MoO₄ ²⁻ broadened the dead zone and decreased the growth rate of (100) face of KDP crystals. The growth kinetic analysis in terms of two-dimensional nucleus and screw dislocation models implied that the energetic parameter γ/kT decreased with an increase of MoO₄ ²⁻ concentration. The influence of MoO₄ ²⁻ growth steps on (100) face of KDP crystal was observed through ex situ AFM technique. It gave evidence that MoO₄ ²⁻ could postpone the step bunching and make the step edge curving and knaggy to reduce the edge free energy, which was in agreement with the growth kinetics calculations. Additionally, the poisoned mechanism of MoO₄ ²⁻ and Fe³⁺ on step morphologies was detailed contrasted. The interaction process was discussed according to electro negativity analysis, which indicated MoO₄ ²⁻ (actually were HMoO₄ ⁻ and H₂MoO₄) could be absorbed onto (100) face through charge-assisted hydrogen bonds and caused more Mo element distributed in prismatic sector.     

Preparation and characterization of some single,mixed and doped crystals and instrumentation aspects

The preparation and characterization (salient ones) of KAl (SO₄)₂. 12H₂O, KCr (SO₄)₂·12H₂O, mixed crystals of both with 10 to 90% of each component, mixed crystals of CsCl with CuCl₂, doped crystals of KBr with K₃FeCN₆, mixed crystals (NH₄)₂SO₄ with CuSO₄ or NiSO₄, NaCl with growth improver Pb⁺², Mn⁺², metallic crystals of Zn, Bi, ionic crystals of alkali halides with Pb⁺², or Cd⁺², etc. are presented. Instrumentation aspects of a rotary crystallizer, a homogeniser, an ingot release mechanism and a zone refiner are shown.     

Biomimetic mineralization of calcium phosphate crystals in polyacrylamide hydrogel: Effect of concentrations of calcium and phosphate ions on crystalline phases and morphology

Calcium phosphate crystals were synthesized in polyacrylamide (PAAm) hydrogel, and the effects of the concentrations of calcium and phosphate ions on the crystalline phases and morphology were investigated. PAAm hydrogels containing diammonium hydrogen phosphate ((NH₄)₂HPO₄) were transformed into calcified materials by diffusion of calcium ions from calcium nitrate (Ca(NO₃)₂) aqueous solution into the gels. Several kinds of calcium phosphate crystals were precipitated at various Ca(NO₃)₂ concentrations (0.5–4.0 mol·dm^? 3), or (NH₄)₂HPO₄ contents (3.6–21.6 mmol) in the gels. The crystalline phases were mainly determined by the (NH₄)₂HPO₄ content in the gels. When the (NH₄)₂HPO₄ content was ≥ 10.8 mmol, hydroxyapatite (HAp) formed near the interfaces between Ca(NO₃)₂ solution and the gels, whereas octacalcium phosphate (OCP) formed in gels with ≤ 10.8 mmol (NH₄)₂HPO₄. HAp crystals were granular in form and about 200 nm in diameter, and OCP crystals were spherulitic with diameter 10–70 μm.     

Linear and nonlinear optical properties of KDP crystals with incorporated Al2O3⋅nH2O nanoparticles

Optical and nonlinear optical properties of a novel composite system based on KDP single crystals with embedded nanoparticles of nanostructured oxyhydroxide of aluminum (Al₂O₃·nH₂O, NOA), were studied. KDP crystals with NOA nanoparticles (KDP:NOA) possess high optical quality and homogeneity. Optical spectroscopy showed the presence of an absorption band at 270 nm caused by NOA nanoparticles incorporated in the KDP matrix. There was observed an enhancement of nonlinear refractive index and inversion of its sign in KDP:NOA crystals in comparison with nominally pure KDP crystals under excitation of picosecond laser pulses. The obtained results demonstrate that KDP:NOA is a promising composite material for optoelectronics and nonlinear optics.     

Solution growth of KDP single crystals doped with titanium dioxide nanoparticles

Pure KDP single crystals and KDP crystals doped with TiO₂ nanocrystals were grown by the method of temperature reduction from aqueous solutions. Adsorption of the phosphate-ions on the surface of TiO₂ particles was studied by FTIR spectroscopy. It was shown that the nanoparticles with adsorbed H₂PO₄^– and (H₂PO₄)₂^2–anions were incorporated predominantly into the positively charged face (1 0 1) of the pyramidal sector of KDP. High-resolution X-ray three-crystal diffractometry (TCD) investigation of the as grown samples of KDP + TiO₂ revealed the presence of the turns of the growth layer “stacks” up to 3 arcsec in the growth sectors {1 0 0} and {1 0 1}. The observed thickness of these “stacks” was of the order of 20–30 μm. For KDP + TiO₂ crystals there was found a relative change of the crystal lattice parameter (Δd/d) caused by incorporation of TiO₂ nanoparticles into the boundaries of the growth layers. This gave rise to the formation of a semicoherent binding on the interface between the captured TiO₂ and the matrix. No essential influence of the nanoparticles on the laser damage threshold of KDP with 10⁻⁵ wt.% of TiO₂ was established.     

Preparation of hydroxyapatite ceramics by hydrothermal hot-pressing method at 300 °C

Hydroxyapatite (HA) ceramics were prepared by a hydrothermal hot-pressing (HHP) method at a low temperature (300 °C). DCPD (CaHPO₄·2H₂O) + Ca(OH)₂, OCP (Ca₈H₂(PO₄)₆·5H₂O) + Ca(OH)₂, DCPD + NH₃·H₂O, OCP + NH₃·H₂O or α-TCP (Ca₃(PO₄)₂) + NH₃·H₂O were used as the precursors. The mixture was treated by HHP under a condition of 300 °C/40 MPa. In sample DCPD + Ca(OH)₂ and OCP + Ca(OH)₂, the HA ceramics obtained showed a porous and homogenous microstructure, and the bending strength were 9.9 MPa and 10.9 MPa, respectively. In sample α-TCP+NH₃·H₂O, rod-like HA crystals produced. When the starting materials were DCPD + NH₃·H₂O, OCP + NH₃·H₂O, the HA particles produced exhibited plate-like features. It appeared that the plate-like HA particles stacked into a lamellar structure. The formation of the lamellar structure leads to a noticeable improvement in fracture property of the HA ceramic. The bending strength and the fracture toughness of the sample prepared from OCP and ammonia water reach 90 MPa and 2.3 MPam^1/2, respectively.     

Reactively sputtered MoO3 films for ammonia sensing

We report the gas-sensing properties of ion-beam sputter deposited MoO₃ thin-films. The change in the DC conductivity was measured in dry N₂ with 10% O₂ in the presence of up to 490 ppm of NH₃, NO, NO₂, C₃H₆, CO and H₂. At ∼440 °C the film was found to be very sensitive to NH₃, with 490 ppm increasing the conductivity by approximately a factor of 70. This was approximately 17 times greater than the response to the other gases. The NH₃ response was strongly affected by the accompanying levels of O₂, NO₂ and H₂O. For example, changing the accompanying O₂ levels from 1% to 20% decreased the NH₃ response by approximately a factor of 20. Similarly, the presence of 100 ppm NO₂ (in 10% O₂) decreased the NH₃ response by approximately a factor of three, and 1% water vapor decreased it by more than a factor of two. The NH₃ response, however, was relatively unaffected by 100 ppm of accompanying NO, C₃H₆, CO or H₂. XPS measurements show that the increased conductivity in the presence of NH₃ was also accompanied by a partial reduction of the surface MoO₃. We observed an increase in the resistance of the films after extended time at elevated temperatures.     

Synthesis and crystal structure of [UO<Subscript>2</Subscript>(OH)(CO(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>2</Subscript>(ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The complex [UO₂(OH)(CO(NH₂)₂)₃]₂(ClO₄)₂ (I) was synthesized. A single crystal X-ray diffraction study showed that compound I crystallizes in the triclinic system with the unit cell parameters a = 7.1410(2), b = 10.1097(2), c = 11.0240(4) Å, α = 104.648(1)°, β = 103.088(1)°, γ = 108.549(1)°, space group \(P\bar 1\), Z = 1, R = 0.0193. The uranium-containing structural units of the crystals are binuclear groups [UO₂(OH)· (CO(NH₂)₂)₃] ₂ ²⁺ belonging to crystal-chemical group AM²M ₃ ¹ [A = UO ₂ ²⁺ , M² = OH^?, M¹ = CO(NH₂)₂] of uranyl complexes. The crystal-chemical analysis of nonvalent interactions using the method of molecular Voronoi-Dirichlet polyhedra was performed, and the IR spectra of crystals of I were analyzed.     

Characterization and catalytic performance of vanadium supported on sulfated Ti-PILC catalysts issued from different Ti-precursors in selective catalytic reduction of nitrogen oxide by ammonia

Vanadium supported on sulfated Ti-pillared clay catalysts (STi-PILCs) issued from different Ti-precursors were investigated for selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂. The STi-PILCs supports were prepared by hydrolysis of a series of organic or inorganic Ti-precursors; Ti(OCH₃)₄, Ti(OC₂H₅)₄, and TiCl₄ with H₂SO₄, and then modified with vanadium introduced by impregnation method. The unpromoted and promoted vanadium pillared clays were characterized using chemical analysis, N₂-physisorption, NH₃-TPD, H₂-TPR, and tested for SCR of NO by NH₃. It was found that the textural and acidic properties of the STi-PILC materials are influenced by the nature of the Ti-precursor; and the use of Ti-methoxide allows the synthesis of STi-PILC with the highest acidity. The presence of vanadium on STi-PILC supports reduces their surface areas and porous volumes, creates new redox sites, and enhances the reducibility of the sulfate groups leading to better redox properties of the binary V-STi-PILCs. After vanadium addition, the STi-PILC materials issued from Ti(OCH₃)₄, exhibited higher NO reduction activity at high temperature. These results underline the importance of the Ti-precursor for the preparation of the STi-PILC support, and the role of vanadium to increase the redox properties of V-STi-PILC catalyst for the SCR of NO by NH₃.     

Synthesis and crystal structures of a new (2,3-(CH3)2C6H3NH3)H2XO4 (X=P,As)

The aim of encapsulation of 2,3-dimethylanilinium cation in (H₂XO₄)_n polymeric anion chains is to build acentric frameworks that are efficient for non-linear optical (NLO) applications. The synthesis and structures of two new inorganic–organic NLO crystals with general formula (2,3-(CH₃)₂C₆H₃NH₃)H₂XO₄ (X=P, As) are reported. The magnitude of their second harmonic generations (SHG) responses was found to be between the KDP and urea. They crystallize with monoclinic unit-cells and are isotopic. We have determined the structure of phosphoric salt. The following unit-cell parameters were found: a=8.866(3) Å, b=5.909(6) Å, c=10.644(5) Å, β=112.44(1)°, V=515.5(5) Å³ and D_X=1.412 g cm⁻³. The space group is P2₁ with Z=2. The structure was refined with R=0.041 (R_w=0.057) for 1652 reflections with I≥3σ(I). It exhibits infinite (H₂PO₄)_nⁿ⁻ chains. The organic groups (2,3-(CH₃)₂C₆H₃NH₃)⁺ are anchored between adjacent polyanions through multiple hydrogen bonds. Chemical preparation, crystal structure, calorimetric and spectroscopic investigation are described.     

Low temperature phonon thermal conductivity of the quasi-one-dimensional compounds (NbSe4)3I, (TaSe4)2I and K0.3MoO3

We report on measurements of the thermal conductivity of quasi-one-dimensional compounds K_0.3MoO₃, (NbSe₄)₃I, and (TaSe₄)₂I between 0.07K and 4 K. Despite the presence of a charge-density wave, the observed behaviour is similar to that expected in good insulating crystals, where the thermal conductivity well below 1 K is mainly governed by boundary scattering with some degree of specular reflection. However a pronounced anomaly is detected in (TaSe₄)₂I as a sharp maximum around 1 K, followed by a broad minimum around 3 K. We ascribe this anomaly to strong scattering by low-lying transverse acoustic phonons, with a very weak dispersion over a large part of the Brillouin zone, lying at an unusually low frequency.     

Mass spectrometric study of gas-phase chemistry in the hot-wire CVD processes of SiH4/NH3 mixtures

The gas-phase reaction products of SiH₄, NH₃ and their mixtures from a hot-wire CVD chamber were investigated using laser ionization time-of-flight mass spectrometry. Both vacuum ultraviolet laser single photon ionization and laser-induced electron impact ionization were used. The main products observed from a 50% NH₃/He sample were H₂ and N₂. The study of an NH₃/SiH₄ mixture (P_NH3:P_SiH4 = 100:1) has shown that the NH₃ dissociation on the filament was suppressed by the presence of SiH₄ in the system. Signals from Si(NH₂)₄ and Si(NH₂)₃ species were identified as products from the 100:1 NH₃/SiH₄ mixture. The spectrum for a 1:1 NH₃/SiH₄ mixture was dominated by mass peaks characteristic of SiH₄ chemistry in the reactor, i.e. H₂, Si₂H₆, and Si₃H₈, at low temperatures. The extent to which the decomposition of NH₃ is suppressed is enhanced with more SiH₄ molecules in the system.     

Crystal Growth and Electrical Properties of β-CdP<Subscript>2</Subscript> Single Crystals

Optically homogeneous single crystals of tetragonal cadmium diphosphide (β-CdP₂) are prepared by vapor-phase growth, and their electrical conductivity, dielectric permittivity, and loss tangent are measured during slow heating from 78 to 400 K in the [001] and [100] directions at frequencies of 10², 10³, 10⁴, and 10⁶ Hz. The permittivity of the crystals increases with temperature. The electrical properties of β-CdP₂ are shown to be anisotropic.     

Properties of amorphous silica generated by the fluoride method

A study of amorphous silica generated from mineral material by the fluoride method and by different procedures of analysis, i.e., x-ray diffraction, x-ray fluorescence, IR spectroscopy, and nuclear magnetic resonance, is reported. Direct fluoridation of amorphous silica was performed by using gaseous F₂ and different conditions of processing, which allowed us to assess the reduction of impurities in amorphous silica and to show that (NH₄)(Si(NH₃)F₅) was not present in the sample as an impurity.     

Correlation between ionic conductivity and fluidity of polymer gel electrolytes containing NH4CF3SO3

Nonaqueous polymer gel electrolytes containing ammonium triflate (NH₄CF₃SO₃) and dimethylacetamide (DMA) with polymethylmethacrylate (PMMA) as the gelling polymer have been synthesized which show high value of conductivity (~ 10^-2 S/cm) at 25°C. The conductivity of polymer gel electrolytes containing different concentrations of NH₄CF₃SO₃ shows a small decrease with the addition of PMMA and this has been correlated with the variation of fluidity of these gel electrolytes. The small decrease in conductivity with PMMA addition shows that polymer plays the role of stiffener and this is supported by FTIR results which also indicates the absence of any active interaction between polymer and NH₄CF₃SO₃ in these gel electrolytes.     

Charge-Assisted Hydrogen-Bonded Organic Frameworks with Inorganic Ammonium Regulated Switchable Open Polar Sites

Surface open polar sites within the voids of porous molecular crystals define the localized physicochemical environment for critical functions such as gas separation and molecular recognition. This study presents a new charge-assisted hydrogen bonding (H-bonding) motif, by exploiting inorganic ammonium (NH₄⁺) cations as H-bond donors, to regulate the assembly of C₂-symmetric carboxylic tectons for building robust H-bonded frameworks with permanent ultra-micropores and open oxygen sites. Diverse building blocks are bridged by tetrahedral NH₄⁺ to expand distinctive H-bonded networks with varied pore architectures. Particularly, the open polar oxygen sites can be switched by altering NH₄⁺ sources to tune the deprotonation of carboxyl-containing tectons. The activated porous PTBA·NH₄·DMF preserves the pore architecture and open polar oxygen sites, exhibiting remarkably selective sorption of CO₂ (107.8 cm³ g⁻¹,195 K) over N₂ (11.2 cm³ g⁻¹, 77 K) and H₂ (1.4 cm³ g⁻¹, 77 K).     

Variation of the An-O bond lengths in NaAnO2(OOCCH3)3 and (NH4)4AnO2(CO3)3, An = U(VI), Np(VI), and Pu(VI)

For studying actinide contraction in triacetate and tricarbonate complexes of hexavalent actinides in the series U-Np-Pu, single crystals were prepared and crystal structures of NaPuO₂(OOCCH₃)₃ and (NH₄)₄. AnO₂(CO₃)₃ (An = Np, Pu) were determined. These compounds are isostructural with NaAnO₂(OOCCH₃)₃ (An = U, Np) and (NH₄)₄UO₂(CO₃)₃ studied previously. The coordination surrounding of An(VI) is a distorted hexagonal bipyramid. The actinide contraction in An(VI) triacetate and tricarbonate complexes is manifested in shortening of the bond lengths in the AnO ₂ ²⁺ cation in the series U-Np-Pu. In triacetate complexes NaAnO₂(OOCCH₃)₃, the average bond lengths in AnO ₂ ²⁺ decrease by approximately 2.3% in passing from Np(VI) to Pu(VI). In tricarbonate complexes (NH₄)₄AnO₂(CO₃)₃, the bond lengths in AnO ₂ ²⁺ decrease by approximately 0.7% in passing from U to Np and by approximately 0.4% in passing from Np to Pu. The actinide contraction is less noticeable in the equatorial planes of the bipyramids. The lengths of the An-O bonds with oxygen atoms located around actinyl groups depend on the ligand nature and also on participation of oxygen atoms in the coordination with Na⁺ cations in the triacetate complexes or in hydrogen bonds with NH ₄ ⁺ ions in the tricarbonate complexes. Original Russian Text ? I.A. Charushnikova, N.N. Krot, Z.A. Starikova, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 6, pp. 495–499.     

DTA measurements of normal-incommensurate phase transition in (NH4)2ZnCl4 and K2ZnCl4 crystals

Differential thermal analysis (DTA) was applied to determine the changes in enthalpy and entropy of (NH₄)₂ZnCl₄ and K₂ZnCl₄ crystals at their phase transition from the orthorhombic normal phase to the incommensurate phase. The temperature of this transition, T _i , is 406 K for (NH₄)₂ZnCl₄ and 555 K for K₂ZnCl₄ and the entropy changes (S/R) are 0.053 and 0.035, respectively. The low value obtained for S/R is characteristic of incommensurate phase transitions. The results were compared with the data reported for other crystals of the A₂BX₄ family. Thermal properties of the crystals of the A₂ZnCl₄ subgroup were found to the correlated with the length of A-Cl bonds.